Synthesis of a Metal–Organic Framework Material,Iron Terephthalate,by Ultrasound,Microwave, and Conventional Electric Heating: A Kinetic Study

A metal–organic framework material named MIL‐53(Fe), iron terephthalate, has been synthesized sovothermally at a relatively low temperature by not only conventional electric (CE) heating, but also by irradiation under ultrasound (US) and microwave (MW) conditions to gain an understanding of the accelerated syntheses induced by US and MW. The kinetics for nucleation and crystal growth were analyzed by measuring the crystallinity of MIL‐53(Fe) under various conditions. The nucleation and crystal growth rates were estimated from crystallization curves of the change in crystallinity with reaction time. The activation energies and pre‐exponential factors were calculated from Arrhenius plots. It was confirmed that the rate of crystallization (both nucleation and crystal growth) decreases in the order US>MW?CE, and that the accelerated syntheses under US and MW conditions are due to increased pre‐exponential factors rather than decreased activation energies. It is suggested that physical effects such as hot spots are more important than chemical effects in the accelerated syntheses induced by US and MW irradiation. The syntheses were also conducted in two steps to understand quantitatively the acceleration induced by MW and it was found that the acceleration in crystal growth is more important than the acceleration in nucleation, even though both processes are accelerated by MW irradiation.     

Dechlorination of poly(vinyl chloride) by microwave irradiation I: A simple examination using a commercial microwave oven

Poly(vinyl chloride) (PVC) was decomposed by microwave (MW) irradiation (2.45 GHz) using a commercial MW oven. The efficiency of dielectric absorption was evaluated quantitatively from the rate of temperature increase on MW irradiation. The efficiency of dielectric heating increased at temperatures above the glass transition temperature (T_g). The decomposition on MW irradiation, monitored using the weight, depended on the initial (preheating) temperature of the sample before irradiation. The degradation time profile with various initial temperatures was shifted along the time axis and was successfully superimposed on a single curve. A pure PVC film was subjected to heating at a constant temperature from 230 °C to 310 °C, and the rate of weight decrease on heating was measured. The apparent activation energy was 84.4 kJ/mol for a single monomer unit.     

Acylation and related reactions under microwaves. 4. Sulfonylation reactions of aromatics.

Solvent-free sulfonylation of benzene and its activated or deactivated derivatives were carried out under microwave (MW) irradiation and a catalytic amount of iron(III) chloride, which, under these conditions, is more active than other metallic salts. With more reactive and/or nonvolatile reagents (anisole, xylenes, mesitylene) expeditious conditions (short reaction time at constant MW power without control of the temperature) were used. With less reactive and/or low-boiling reagents (benzene, toluene, halobenzenes), the rise in temperature and the increase of reaction time were controlled either by sequential MW irradiation or by a temperature order. It was shown that MWs cause preferential interactions with polar species present in the reaction, especially the aryl sulfone and its FeCl3-complexed form. A MW nonthermal effect was not observed when identical temperature gradients were produced by classical heating and MW irradiation, and if reaction temperature was strictly controlled.     

Influence of microwave irradiation on enzyme kinetics

The in vitro effect of 2.45 GHz microwave irradiation on porcine pepsin activity under controlled temperature and absorbed microwave power via kinetic parameters was evaluated. Kinetic study with respect of time of irradiation demonstrated the existence of an inactivation effect of microwaves at pH 2 on pepsin molecule. Bovine serum albumin (BSA)-bromphenol blue (BPB) complex was used as substrate for the assay of pepsin by kinetic method. Depending on absorbed microwave dose, the degree of caused inactivation varies from 39.11 to 45.91% for 5 and 20 min of pepsin MW irradiation, respectively. The V _maxapp and K _mapp were calculated for low (5 min of MW irradiation) and higher specific absorbed dose (20 min of MW irradiation), as well as for untreated enzyme, from double reciprocal Lineweaver-Burk plot. The effect of microwaves on substrate (BSA-BPB complex) was also investigated. For reaction performed with MW irradiated substrate for 5 min the reaction rate was decreased for 15.15%, while for 20 min of substrate irradiation reaction rate was decreased for 25.52% compared to the control reaction. The article is published in the original.     

Endocyclic cleavage in glycosides with 2,3-trans cyclic protecting groups

An endocyclic pathway is proposed as a reaction mechanism for the anomerization from the β (1,2-trans) to the α (1,2-cis) configuration observed in glycosides carrying 2,3-trans cyclic protecting groups. This reaction occurs in the presence of a weak Lewis or Br?nsted acid, while endocyclic cleavage (endocleavage) in typical glycosides was observed only when mediated by protic media or strong Lewis acids. To rationalize the behavior of this class of compounds, the reaction mechanism and the promoting factors of the endocleavage are investigated using quantum-mechanical (QM) calculations and experimental studies. We examine anomerization reactions of thioglycosides carrying 2,3-trans cyclic protecting groups, employing boron trifluoride etherate (BF(3)·OEt(2)) as a Lewis acid. The estimated theoretical reactivity, based on a simple model to predict transition state (TS) energies from the strain caused by the fused rings, is very close to the TS energies calculated by the TS search along the C1-C2 bond rotation after the endo C-O bond breaking. Excellent agreement is found between the predicted TS energies and the experimental reactivity ranking. The series of calculations and experiments strongly supports the predominance of the endocyclic rather than the exocyclic mechanism. Furthermore, these investigations suggest that the inner strain is the primary factor enhancing the endocleavage reaction. The effect of the cyclic protecting group in restricting the pyranoside ring to a (4)C(1) conformation, extensively discussed in conjunction with the stereoelectronic effect theory, is shown to be a secondary factor.     

Microwave-Assisted Ionic Liquid-Catalyzed Selective Monoesterification of Alkylphosphonic Acids—An Experimental and a Theoretical Study

It is well-known that the P-acids including phosphonic acids resist undergoing direct esterification. However, it was found that a series of alkylphoshonic acids could be involved in monoesterification with C₂–C₄ alcohols under microwave (MW) irradiation in the presence of [bmim][BF₄] as an additive. The selectivity amounted to 80–98%, while the isolated yields fell in the range of 61–79%. The method developed is a green method for P-acid esterification. DFT calculations at the M062X/6–311+G (d,p) level of theory (performed considering the solvent effect of the corresponding alcohol) explored the three-step mechanism, and justified a higher enthalpy of activation (160.6–194.1 kJ·mol⁻¹) that may be overcome only by MW irradiation. The major role of the [bmim][BF₄] additive is to increase the absorption of MW energy. The specific chemical role of the [BF₄] anion of the ionic liquid in an alternative mechanism was also raised by the computations.     

Photocyclization of carvone to carvone camphor using rare gas halide lasers

The intramolecular photocyclization of (-)carvone with rare gas halide lasers is decribed. A 70-fold increase in quantum yield is observed at an intensity of 60 MW/cm², which is rationalized in terms of consecutive two-photon absorption. The mechanism proposed also describes the product distribution, which is different from that obtained by lamp irradiation.     

Refinery of Biomass by Utilization of Specific Effects of Microwave Irradiation

The results of application of microwave (MW) irradiation to achieve refinery of various kinds of recalcitrant biomass were summarized with special emphasis on recent innovative utilization of sensitizers for MW irradiation. The saccharification rates of lignocellulosic plant biomass consisting of softwoods, hardwoods and monocotyledons attained by the simple MW irradiation treatment were in the orders of 35-65% (softwoods), 70-80% (hardwoods) and around 80% (monocotyledons), respectively. The corresponding values of cellulose were around 69-81% (230-240 °C), while xylan was susceptible to the MW energy and easily decomposed into oligomers including xylose by heating at >150 °C, optimally at 204 °C, to give 99% solubility rate. However, the effects of the MW treatment on the agro-food byproducts varied highly depending upon their origins. These results indicate necessity of troublesome specification of the optimum condition for each case. For development of more versatile and comprehensive refinery method we tried to use sensitizers for MW irradiation.We found that hydrogen peroxide was remarkably effective for biomass refinery. Utilization of activated carbon as a sensitizer for MW irradiation was also effective for saccharification of starchy materials. Enhancement of the surface charge of the activated carbons by oxidation and preparation of microwave absorption solid acid catalysts were recommended to further enhance their effectiveness. The overall results showed the importance of four factors, less affinity toward oligosaccharides in relation with pore size, quantity of surface negative charges in addition to electro-conductivity, faster filtration ability and unknown hot spot productivity. Due to removal of the coloured materials by the activated carbons, clear saccharified solution produced by one pot conversion could be directly used for further fermentation to produce biofuels such as ethanol.     

Environmentally Friendly Methods for Syntheses of New Aromatic Bisesters

Two environmentally friendly methods, one in liquid and the other in solid phase, for preparation of phenyl bisesters (bearing alkylating groups) under microwave (MW) irradiation are presented. The MW remarkably enhanced the rate of acceleration for esterification: the reaction time decreased dramatically, the reaction conditions are milder, and the consumed energy decreased considerably. In the most cases, in the liquid phase under MW irradiation, the yields are better, in some cases substantially (almost 75%). In the solid phase under MW irradiation, the yields are moderate to good compared to the liquid phase but excellent compared to conventional heating. Both methods are fast, general, and facile, but because the solid-phase reactions are solvent-free, we consider this one to be the most suitable for synthetic chemistry. A comparative study of MW and conventional heating was done.     

Rapid assessment of the impact of microwave heating coupled with UV-C radiation on the degradation of PAHs from contaminated soil using FTIR and multivariate analysis

The presence and fate of polyaromatic hydrocarbons (PAHs) in the environment are receiving a great concern. In this study, three oil-contaminated soils (industrial area, Dukhan city, and artificial soils) were utilized to examine the effect of microwave (MW) heating and UV-C irradiation on the PAHs degradation. A rapid assessment of the impact was evaluated using Fourier transform infrared (FTIR) and multivariate analysis. The total organic matter values for the maximum PAHs reduction were evaluated based on the FTIR spectra of the contaminated soils followed with the principal component analysis (PCA). The results showed that the highest total organic carbon reduction was achieved for the industrial soil sample that required a high MW power and long MW exposure time. On the other hand, the Dukhan city soil sample, which has the lowest total organic carbon, required a high MW power and short MW exposure time followed by UV-C treatment for 20 min to reach the maximal FTIR transmittance reduction. The cluster analysis was also used to evaluate the impact of MW heating, and MW heating followed by UV-C irradiation on the degradation of PAHs. The PCA results of the industrial city sample showed that neither MW treatment (100% MW, 15 min exposure time) followed by UV-C treatment for 20 min nor 10 min is significantly different from the MW treatment (100% MW, 15 min exposure time). However, for the Dukhan sample, the UV-C treatment at 10 min after high MW power and long exposure time (100% MW, 15 min exposure time) was the most efficient treatment.     

Investigations of glycosylation reactions with 2-N-acetyl-2N,3O-oxazolidinone-protected glucosamine donors

NIS/AgOTf-promoted glycosylations with ethyl 2,3-N,O-carbonyl-2-deoxy-1-thio-beta-D-glucopyranoside donors can be performed with either alpha- or beta-selectivity by tuning the reaction conditions. Small amounts of AgOTf (0.1 equiv) and short reaction times give beta-selectivity, whereas 0.4 equiv of AgOTf and prolonged reaction times afford alpha-linked products. NMR-monitored glycosylation and anomerization experiments show initial formation of exclusively the beta-linkage, which anomerizes, through an intramolecular mechanism involving an endocyclic C-O bond cleavage, to the alpha-linkage.     

Facile Synthesis of new 3,5‐Dispiro Substituted Piperidine Analogs via Microwave‐Assisted One Pot Multicomponent Reaction

An eco‐efficient one‐pot three component reaction for the synthesis of 3,5‐dispirosubstituted piperidines is reported by condensing of 2‐thiobarbituric acid, formaldehyde, and aromatic amines in the presence of a catalytic amount of p‐toluenesulfonic acid (1.0 equivalent) in dimethyl sulfoxide. The reactions were examined by two special methods such as classical heating and microwave (MW) irradiation. In general, improvements in rates and yields were observed when reactions were carried out under MW irradiation compared to the conventional method.     

能源与环境应用中的微波催化研究进展

微波是一种能量传递方式。与传统电加热相比,微波加热具有加热速度快、热惯性小、选择性加热等特点,因而被视为一种优质的能量来源。微波催化是一种使用微波对反应系统供能,从而推动催化反应进行的化学过程。近年来,许多研究者致力于探索和发展微波催化技术,包括利用微波技术提升化学反应速率、开发具有出色微波吸收能力的催化剂、建立节能环保的微波催化系统等。本文首先介绍了微波的相关理论,讲述了材料对微波的吸收原理;然后从微波催化降解挥发性有机物（Volatile Organic Compounds, VOCs）、微波催化污水处理、微波催化生物质热解和微波催化碳氢化合物转化等方面综述了微波催化在能源环境中的应用;最后对微波催化过程的机理展开了讨论。     

Dynamic Nuclear Polarization in the solid state: a transition between the cross effect and the solid effect

Proton Dynamic Nuclear Polarization (DNP) experiments were conducted on a 3.4 T homebuilt hybrid pulsed-EPR-NMR spectrometer, on static samples containing 10 mM or 40 mM TEMPOL in frozen glassy solutions of DMSO/water. During DNP experiments proton-NMR signals are enhanced with the help of microwave (MW) irradiation on or close to the Electron Paramagnetic Resonance (EPR) spectrum of the free radicals in the sample, transferring polarization from the free electrons to the nuclei. In the solid state a distinction is made between three DNP enhancement mechanisms: the Solid Effect (SE), the Cross Effect (CE) and Thermal Mixing (TM). In an effort to determine the dominant DNP mechanisms responsible for the enhancement of the nuclear signals, electron and nuclear spin-lattice relaxation rates, enhancement buildup times and microwave (MW) swept DNP spectra were measured as a function of temperature and MW irradiation strength. We observed lineshape variations of the DNP spectra that indicated changes in the relative contributions of SE-DNP and CE-DNP with temperature and MW power. Using a theoretical model describing the SE-DNP and CE-DNP the DNP spectra could be analyzed without involving the TM-DNP mechanism and the relative SE-DNP and CE-DNP contributions to the nuclear enhancement could be determined. From this analysis it follows that lowering the temperature beyond 20 K increases the SE-DNP and decreases the CE-DNP contributions. Possible explanations for this behavior are suggested.     

Significant Substituent Effect on the Anomerization of Pyranosides: Mechanism of Anomerization and Synthesis of a 1,2‐cis Glucosamine Oligomer from the 1,2‐trans Anomer

Aminoglycosides containing a 2,3‐trans carbamate group easily undergo anomerization from the 1,2‐trans glycoside to the 1,2‐cis isomer under mild acidic conditions. The N‐substituent of the carbamate has a significant effect on the anomerization reaction; in particular, an N‐acetyl group facilitated rapid and complete α‐anomerization. The differences in reactivity due to the various N‐substituents were supported by the results of DFT calculations; the orientation of the acetyl carbonyl group close to the anomeric position was found to contribute significantly to the directing of the anomerization reaction. By exploiting this reaction, oligoaminoglycosides with multiple 1,2‐cis glycosidic bonds were generated from 1,2‐trans glycosides in a one‐step process.     

Photoinitiated RAFT polymerization of vinyl acetate

A photoinitiation process was investigated to develop a rapid and well‐controlled RAFT polymerization method applied to vinyl acetate (VAc) using methyl (ethoxycarbonothioyl)sulfanyl acetate (MESA) and bis(2,4,6‐trimethylbenzoyl)phenylphosphine oxide as the RAFT agent and photoinitiator, respectively. MESA was selected as the photochemically inert RAFT agent to minimize photolysis of the thiocarbonylthio groups during polymerization. Poly(vinyl acetate) with a prespecified well‐controlled molecular weight (MW) and a narrow MW distribution was successfully synthesized. The polymerization reaction proceeded as a living polymerization and was remarkably rapid compared with approaches that use thermally initiated processes with a very short induction period. A detailed kinetic study of the mechanism underlying the polymerization reaction, however, revealed that the chain ends containing xanthate moieties were not perfectly stable upon UV‐irradiation, and they generated radicals via homolytic cleavage. This reaction appeared to proceed by a combination of a degenerative transfer RAFT mechanism and a dissociation‐combination mechanism. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Green chemical syntheses and applications within organophosphorus chemistry

Application of the microwave (MW) technique offers many advantages in organophosphorus syntheses. Reluctant reactions may take place on MW irradiation. In most cases, MWs make the reactions more efficient in respect of rate, selectivity and yield. The benefits are shown via representative examples. MW irradiation may replace a catalyst, or simplify catalytic systems. The synthesis of catalysts incorporating heterocyclic P-ligands is also discussed. Where it was relevant, structural chemical details were also provided.     

Microwave-assisted synthesis of metallic nanostructures in solution

Microwave (MW) rapid heating has received considerable attention as a new promising method for the one-pot synthesis of metallic nanostructures in solutions. In this concept, advantageous application of this method has been demonstrated by using some typical examples for the preparation of Ag, Au, Pt, and AuPd nanostructures. Not only spherical nanoparticles, but also single crystalline polygonal plates, sheets, rods, wires, tubes, and dendrites were prepared within a few minutes under MW heating. Morphologies and sizes of nanostructures could be controlled by changing various experimental parameters, such as the concentration of metallic salt and surfactant polymer, the chain length of the surfactant polymer, the solvent, and the reaction temperature. In general, nanostructures with smaller sizes, narrower size distributions, and a higher degree of crystallization were obtained under MW heating than those in conventional oil-bath heating. The origin of these characteristic features under MW irradiation is discussed in terms of thermal and non-thermal effects under MW irradiation.     

Microwaves as “Co-Catalysts” or as Substitute for Catalysts in Organophosphorus Chemistry

The purpose of this review is to summarize the importance of microwave (MW) irradiation as a kind of catalyst in organophosphorus chemistry. Slow or reluctant reactions, such as the Diels-Alder cycloaddition or an inverse-Wittig type reaction, may be performed efficiently under MW irradiation. The direct esterification of phosphinic and phosphonic acids, which is practically impossible on conventional heating, may be realized under MW conditions. Ionic liquid additives may promote further esterifications. The opposite reaction, the hydrolysis of P-esters, has also relevance among the MW-assisted transformations. A typical case is when the catalysts are substituted by MWs, which is exemplified by the reduction of phosphine oxides, and by the Kabachnik–Fields condensation affording α-aminophosphonic derivatives. Finally, the Hirao P–C coupling reaction may serve as an example, when the catalyst may be simplified under MW conditions. All of the examples discussed fulfill the expectations of green chemistry.     

微波无极紫外光助双氧水处理活性艳红X-3B染料废水研究

活性艳红X-3B(C.I.ReactionRed 2)是一种单偶氮染料,其应用范围广泛,可用于棉、粘纤、涤/棉、锦纶、蚕丝、羊毛、锦/粘等织物的染色和丝绸的印花,因此其废水量大且色度深。目前染料废水的生物处理方法脱色效果差、占地面积大、处理周期长,传统的物理法和化学法也存在着成本高、不能彻底矿化染料分子等缺点。近年来发展起来的光化学处理染料废水的方法及各种光化学组合技术日益受到人们关注,但其中使用的普通紫外灯存在使用寿命短、启动慢、发光不稳定、电极材料易损等缺点[1],致使光化学方法处理废水的成本很高。本文利用微波产生的高频…